2
538
M. Desroses et al. / Tetrahedron: Asymmetry 13 (2002) 2535–2539
1
1
09.6, 109.9 (C , iPrd), 128.2, 128.7 (CH-Ar), 126.2,
J1a–1b=9.8, H-1b), 4.03–4.11 (m, 3H, H-3, H-6), 4.16–
4.23 (m, 2H, H-5, H-1a), 4.36 (dd, 1H, J3–4=7.9,
IV
26.3, 137.1, 139.2, 139.3 (C -Ar), 158.8, 158.9 (C -
IV
+
IV
+
CꢀN). MS: m/z 448.5 [M+H] , 465.5 [M+NH ] , 470.5
J4–5=5.3, H-4), 6.20 (d, 1H, H-5i), 6.88 (s, 2H, H-Ar).
4
+
+
13
[
4
M+Na] , 486.5 [M+K] . HRMS: C H NO : calcd
C NMR l 20.2, 21.5 (3×Me), 26.6, 26.8, 26.9, 28.7
(4×iPrd), 46.2 (C-4i), 60.6 (C-6), 72.2 (C-1), 73.3, 74.4,
8.1 (C-3, C-4, C–5), 101.9 (C-5i), 104.9 (C-2), 109.7,
24
33
7
47.2257; found: 447.2249.
7
4
.5. 5-[6-(1,2:3,4-Di-O-isopropylidene-a-
D
-galacto-
112.3 (2×C , iPrd), 128.8 (2×CH-Ar), 125.6, 137.1, 139.3
IV
+
pyranosyloxy)]-3-(3,4,5-trimethoxyphenyl)-4,5-dihy-
droisoxazoles, 6c
(4×C -Ar), 159.1 (C -CꢀN). MS: m/z 448.5 [M+H] ,
IV
IV
+
+
470.5 [M+Na] , 486.5 [M+K] . HRMS: C H NO :
2
4
33
7
calcd 447.2257; found: 447.2247.
Column chromatography afforded (50% yield from 3) a
1
1
1
:1 mixture of 6c, as a colorless gum: H NMR l 1.29
minor: [h] −153 (c 0.34, CHCl ). H NMR l 1.37 (s, 3H,
D 3
(
(
s, iPrd), 1.31 (s, iPrd), 1.32 (s, iPrd), 1.42 (s, iPrd), 1.43
s, iPrd), 1.49 (s, iPrd), 1.54 (s, iPrd), 3.26 (dd, J4ib–5i=2.1,
J4ia–4ib=18.1, H-4ib), 3.29 (dd, J4ib–5i=2.1, H-4ia), 3.37
dd, J4ia–5i=5.7, H-4ia), 3.86 (s, OMe), 3.71–4.09 (m,
H-5, H-6a, H-6b), 4.18 (d, J3–4=7.5, J4–5 <0.5, H-4), 4.25
dd, J3–4=7.5, J4–5=1.7, H-4), 4.29 (dd, J1–2=5.1, J2–3
.5, H-2), 4.31 (dd, J1–2=5.1, J2–3=2.5, H-2), 4.57 (dd,
iPrd), 1.42 (s, 3H, iPrd), 1.51 (s, 3H, iPrd), 1.54 (s, 3H,
iPrd), 2.21 (s, 6H, Me), 2.29 (s, 3H, Me), 3.00 (d, 1H,
J4ia–4ib=17.9, H-4ib), 3.32 (dd, 1H, J4ia–5i=6.4, H-4ia),
3.87–4.21 (m, 6H, H-1a, H-1b, H-3, H-5, H-6a, H-6b),
4.51 (dd, 1H, J3–4=6.0, J4–5=6.0, H-4), 5.91 (d, 1H,
(
+
(
=
H-5i), 6.89 (s, 2H, H-Ar). MS: m/z 448.5 [M+H] , 470.5
+
2
[M+Na] .
J2–3=2.5, J3–4=7.5, H-3), 4.60 (dd, J2–3=2.5, J3–4=7.5,
H-3), 5.50 (d, J1–2=5.1, H-1), 5.53 (d, J1–2=5.1, H-1),
4.8. (5RS)-5-[3-(1,2:4,5-Di-O-isopropylidene-b-D-
fructopyranosyloxy)]-3-(3,4,5-trimethoxyphenyl)-4,5-
dihydroisoxazoles, 7c
13
5
.73 (dd, H-5%), 6.88 (s, H-Ar), 6.89 (s, H-Ar). C NMR
l 24.8, 24.9, 25.3, 25.4, 26.3, 26.5 (iPrd), 42.2 (C-4i), 56.6,
6.7, 61.3 (OMe), 66.1, 66.9 (C-5), 68.1, 68.2 (C-6), 70.1,
0.7 (C-3), 70.9, 71.0 (C-2), 71.1, 71.7 (C-4), 96.7, 96.8
Column chromatography afforded (70% yield from 4) a
10:1 mixture of 7c, as a colorless gum: major: [h] +4 (c
D
1
2.6, CHCl ). H NMR l 1.25 (s, 3H, iPrd), 1.39 (s, 3H,
IV
3
1
24.9, 140.3, 140.4, 153.7 (C -Ar), 157.3, 157.4 (C -
iPrd), 1.46 (s, 3H, iPrd), 1.63 (s, 3H, iPrd), 3.26 (d, 1H,
J4ib–5i <0.5 Hz, J4ia–4ib=17.0 Hz, H-4ib), 3.42 (dd, 1H,
J4ia–5i=4.9 Hz, H-4ia), 3.89–4.33 (m, 16H, H-1a, H-1b,
H-3, H-4, H-5, H-6a, H-6b, OMe), 6.15 (d, 1H, H-5i),
IV
+
IV
+
CꢀN). MS: m/z 496.5 [M+H] , 513.5 [M+NH ] , 518.5
4
+
+
[
4
M+Na] , 534.5 [M+K] . HRMS: C H NO : calcd
24 33 10
95.2104; found: 495.2111.
13
6
.91 (s, 2H, H-Ar). C NMR (67.5 MHz, CDCl ) l 26.1,
3
4
.6. (5RS)-5-[3-(1,2:4,5-Di-O-isopropylidene-b-
D
-
27.4, 28.6, 29.9 (4×iPrd), 42.2 (C-4i), 56.6 (OMe), 60.2
(C-6), 61.2 (OMe), 71.7 (C-1), 73.2, 74.3, 77.9 (C-3, C-4,
C-5), 102.3 (C-2), 102.8 (C-5i), 104.2, 104.6 (2×CH-Ar),
109.6, 110.6 (2×C , iPrd), 122.8, 138.7, 151.9 (4×C -
fructopyranosyloxy)]-3-phenyl-4,5-dihydroisoxazoles 7a
Column chromatography afforded (73% yield from 4)
both epimers of 7a in a 10:1 ratio (determined from crude
product), the major isomer being the only product
isolated as a colorless gum: major: [h] +5 (c 2.6, CHCl ).
IV
IV
+
Ar), 156.0 (C -CꢀN). MS (IS): m/z 496.5 [M+H] , 518.5
[M+Na] , 534.5 [M+K].
IV
+
D
3
1
1
H NMR (250 MHz, CDCl ) l 1.22 (s, 3H, iPrd), 1.39
minor: [h] −0.75 (c 0.2, CHCl ). H NMR l 1.30 (s, 3H,
3
D
3
(
(
s, 3H, iPrd), 1.44 (s, 3H, iPrd), 1.62 (s, 3H, iPrd), 3.27
d, 1H, J4ib–5i <0.5, J4ia–4ib=17.2, H-4ib), 3.41 (dd, 1H,
iPrd), 1.40 (s, 3H, iPrd), 1.47 (s, 3H, iPrd), 1.63 (s, 3H,
iPrd), 3.44 (d, 1H, J4ia–4ib=17.6, H-4ib), 3.60 (dd, 1H,
J4ia–5i=5.7, H-4ia), 3.40–4.36 (m, 16H, H-1a, H-1b, H-3,
H-4, H-5, H-6a, H-6b, OMe), 6.13 (d, 1H, H-5i), 6.91 (s,
J4ia–5i=6.1, H-4ia), 3.93–4.20 (m, 6H, H-1a, H-1b, H-3,
H-5, H-6a, H-6b), 4.34 (dd, 1H, J3–4=5.9, J4–5=7.2,
H-4), 6.15 (d, 1H, H-5i), 7.41–7.45 (m, 2H, H-Ar),
+
+
2H, H-Ar). MS (IS): m/z 496.5 [M+H] , 518.5 [M+Na] .
13
7
.65–7.68 (m, 3H, H-Ar). C NMR (67.5 MHz, CDCl )
HRMS: C H NO : calcd 495.2104; found: 495.2098.
3
24 33
10
l 27.5, 28.3, 29.1, 30.3 (4×iPrd), 43.8 (C-4i), 60.2 (C-6),
7
1
1
1.7 (C-1), 73.3, 73.7, (C-3, C-5), 77.9 (C-4), 102.7 (C-5i),
4.9. (5RS)-5-[3-(1,2:4,5-Di-O-isopropylidene-b-D-
03.6 (C-2), 109.3, 112.0 (2×C , iPrd), 127.3, 129.1,
psicopyranosyloxy)]-3-phenyl-4,5-dihydroisoxazoles, 8a
IV
34.5 (5×CH-Ar), 130.2 (C -Ar), 168.5 (C -CꢀN).MS
IV
IV
+
+
+
(
IS): m/z 423.5 [M+NH ] , 428.5 [M+Na] , 444.5 [M+K] .
Column chromatography afforded (55% yield from 5),
both epimers of 8a in a 3:1 ratio, as a colorless gum:
4
HRMS: C H NO : calcd 405.1787; found: 405.1790.
2
1
27
7
1
major: [h] +53 (c 2.9, CHCl ). H l 1.28 (s, 6H, iPrd),
D
3
4
.7. (5RS)-5-[3-(1,2:4,5-Di-O-isopropylidene-b-
D
-
1.40 (d, 6H, iPrd), 3.38–3.50 (m, 2H, J4ia–4ib=5.1 Hz,
H-4i), 3.70–3.90 (m, 2H, J6a–6b=11.5 Hz, H-6), 3.92 (d,
fructopyranosyloxy)]-3-mesityl-4,5-dihydroisoxazole, 7b
1H, J1a–1b=9.3 Hz, H-1a), 4.15 (d, 1H, J3–4=2.2 Hz,
Column chromatography afforded (93% yield from 4)
both epimers of 7b in a 28:1 ratio (determined from crude
H-3), 4.30 (d, 1H, H-5), 4.38 (d, 1H, H-1b), 4.55 (dd, 1H,
J4–5=7.8 Hz, H-4), 5.95 (dd, 1H J5i–4i=5.1 Hz, H-5i,),
7.35–7.45 (m, 3H, H-Ar), 7.63–7.7 (m, 2H, H-Ar).
product), as colorless gums: major: [h]D +142 (c 1.5,
1
13
CHCl ). H NMR l 1.36 (s, 3H, iPrd), 1.39 (s, 3H, iPrd),
C NMR l 23.4, 24.2, 24.7 and 25.3 (4×iPrd), 40.4
3
1
2
.47 (s, 3H, iPrd), 1.64 (s, 3H, iPrd), 2.23 (s, 6H, Me),
.28 (s, 3H, Me), 3.04 (dd, 1H, J4ib–5i <0.5, J4ia–4ib=17.9,
(C-4i), 61.6 (C-6), 70.3 (C-1), 72.6, 72.7 and 73.0 (C-3,
C-4 and C-5), 102.5 (C-5i), 104.3(C-2), 107.6 (CIV iPrd),
108.7 (CIV iPrd), 124.8, 125.5, 127.3 and 129.1
H-4ib), 3.28 (dd, 1H, J4ia–5i=6.2, H-4ia), 3.97 (d, 1H,